CN107602802A - A kind of sofa artificial leather middle foaming layer solvent-free polyurethane resin and preparation method thereof - Google Patents

A kind of sofa artificial leather middle foaming layer solvent-free polyurethane resin and preparation method thereof Download PDF

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CN107602802A
CN107602802A CN201710856325.3A CN201710856325A CN107602802A CN 107602802 A CN107602802 A CN 107602802A CN 201710856325 A CN201710856325 A CN 201710856325A CN 107602802 A CN107602802 A CN 107602802A
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solvent
parts
polyurethane resin
component
free polyurethane
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李晓飞
王海峰
孔为青
范仁祥
姚克俭
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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HEFEI ANLI POLYURETHANE NEW MATERIAL CO Ltd
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Abstract

The invention discloses a kind of sofa artificial leather middle foaming layer solvent-free polyurethane resin and preparation method thereof, and it is by component A and component B in mass ratio 1:2‑2:1 mixes.Any organic solvent is free of in solvent-free polyurethane resin prepared by the present invention, it is green, soft, plentiful as synthetic leather prepared by intermediate layer, and its physical property reaches normal temperature and deflects 100,000 times and do not ftracture, cold-resistant 10 DEG C deflect for 80,000 times and not to ftracture, peel strength is more than 50N/3cm, 70 DEG C, under the conditions of 95% humidity constant temperature and humidity 57 weeks peel strength retention rates up to 75%.

Description

A kind of sofa artificial leather middle foaming layer solvent-free polyurethane resin and preparation method thereof
Technical field
The invention belongs to functional urethane synthetic leather field, and in particular to be sent out among a kind of soft plentiful sofa artificial leather Alveolar layer solvent-free polyurethane resin and preparation method thereof.
Background technology
Polyurethane occupies critical role in material industry, developed into as novel and multifunctional high polymer material One of six big synthetic material of the world.Wherein solvent borne polyurethane is widely used in synthetic leather field and gradually substitutes PVC artificial leather, its Wet processing utilizes solvent and water in polyurethane resin to replace, can not form homogeneous phase because polyurethane resin is not soluble in water and Cohesion shaping；In addition, drying forms loose porous structure after solvent is replaced by water, make soft plentiful to compare PVC artificial leather Closer to corium.But the Synthetic Leather of this wet processing needs largely to use DMF etc. is poisonous to have in process of production Solvent is done harm to, DMF residuals are serious in the synthetic leather prepared.
In numerous polyurethane branch fields, polyurethane foam accounts for the 60% of polyurethane total output.It is mainly characterized by With porous, relative density is small, specific strength is high.The density size and soft or hard degree of polyurethane foam with raw material and can match somebody with somebody Side difference and change, applied to each technology field in national economy, especially in furniture, bed accessory, transport, refrigeration, building etc. Department's use is very universal.Polyurethane foam was gradually applied to synthetic leather industry, the solvent-free poly- ammonia of expansion type bi-component in recent years Ester resin is transported by low-pressure casting machine, stirred, coated in the abscess on dry method surface layer, carrying out foamable reaction formation uniform and smooth Layer, be dried into baking oven it is half-dried, stick Bu Ji enter back into baking oven curing shaping.The feel of synthetic leather made from this technique can be with Conventional wet synthetic leather compares favourably, and common finished leather of dry process production line can, during poisonous have without using any Evil solvent, save wet method process production efficiency height.
All be on the market polyethers system mostly for the expansion type double component solvent-free polyurethane resin of synthetic leather, have compared with Good perforate performance, anti-hydrolytic performance, resistance to low temperature, anti-mildew become performance.But the mechanical strength of polyethers system polyurethane resin Relatively low, obtained synthetic leather peel strength is not high, and polarity and surface layer differ greatly causes interface cohesion loosely.
So with subdivision of the people to sofa artificial leather species and the raising of performance requirement, it is necessary to which a kind of have feel soft simultaneously The soft plentiful and excellent polyurethane resin of peel strength.
The content of the invention
A kind of the present invention is intended to provide sofa artificial leather middle foaming layer solvent-free polyurethane resin and preparation method thereof.This is poly- Urethane resin is without any organic solvent, energy consumption is low, production efficiency is high, disclosure satisfy that downstream client and consumer's sofa synthetic leather Feel, outward appearance, performance etc. require.
Technical scheme is as follows：
A kind of sofa artificial leather middle foaming layer solvent-free polyurethane resin, it is by component A and component B in mass ratio 1:2- 2:1 mixes；
The component A is made up of following raw materials by weight portion：
Polyether polyester copoly type oligomer dihydric alcohol 80-99 parts
Chain extender 1-5 parts
Crosslinking agent 0-1 parts
Water 0.1-3 parts
Catalyst 0.02-1 parts
Foam stabiliser 0-2 parts
Stabilizer 0.5-2.0 parts；
The component B is made up of following raw materials by weight portion：
Polypropylene oxide glycol 40-70 parts
Isocyanates 30-60 parts
Stabilizer 0.5-1.0 parts.
Further scheme, the polyether polyester copoly type oligomer dihydric alcohol is to be esterified dehydration by weight by following component Condensation reaction and be made, its molecular weight is 2000-3000,
Further scheme, the polyether Glycols are molecular weight 400-2000 polypropylene oxide glycol；
The catalyst is butyl titanate or tetraisopropyl titanate；
The small molecule glycol chain extender is ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,4- butanediols, 1,5- Pentanediol, neopentyl glycol, diglycol, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD, 1,4 cyclohexane dimethanol hydrogen One or more in double (2- ethoxys) ethers of quinone.
Further scheme, the crosslinking agent are one or both of glycerine, trimethylolpropane；
The molecular weight of the polypropylene oxide glycol is 1000-3000；
The catalyst is delaying type catalyst；
The foam stabiliser is polyether-modified organic silicon surfactant；
The stabilizer is ultra-violet absorber, hindered amine light stabilizer or antioxidant；
The isocyanates is 4,4 '-methyl diphenylene diisocyanate, 2,4- methyl diphenylene diisocyanates and 4, The mixture of 4 '-methyl diphenylene diisocyanate, or methyl diphenylene diisocyanate and the more isocyanides of polyphenyl polymethylene The mixture of acid esters.
Preferably, the delaying type catalyst is selected from BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228th, Borchi Kat 22, Borchi Kat 24, BiCAT 4130, BiCAT 4232, MB20 and above-mentioned organic metal class Phenolate, formates, hydrochloride one kind therein of catalyst；
The polyether-modified organic silicon surfactant includes DC-193, DC-2525, DC- of US Air gasification work 2585th, B-8715-LF2, B-8726-LF2, B-8738-LF2 of DC-3042, DC-3043, DC-5043 or German Ying Chuan companies, Or L-580, L-818, L-3002, L-3415 of Mai Tu company of the U.S.；
The ultra-violet absorber is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234；Hindered amines light Stabilizer is 292,622,770,944,5050,5060 or 5151；Antioxidant be 245,1010,1035,1076,1098 or 3114；
Another goal of the invention of the present invention is to provide a kind of above-mentioned sofa artificial leather middle foaming layer with no-solvent polyurethane tree The preparation method of fat, it comprises the following steps：
(1) polyether polyester copoly type oligomer dihydric alcohol is prepared：
Magnetic stirring apparatus, thermometer, N will be housed2The four-hole boiling flask of inlet tube and air-cooling condenser pipe is arranged on sheathing In formula resistance heater, polyether Glycols, small molecule dihydric alcohol, adipic acid are added into flask, leads to nitrogen and excludes in flask Air；Then heating is gradually heated up under nitrogen protection and carries out dehydrating polycondensation reaction, and the top of condenser pipe is controlled in temperature-rise period Portion's temperature is less than 100 DEG C；Detection acid number adds catalyst when being not more than 30mgKOH/g continues after reacting 30 minutes, then gradually adds Heat is warming up to 240 DEG C, vacuum >=0.095MPa, and continuing reaction makes hydroxyl value reach 36-56mg KOH/g, and obtained molecular weight is 2000-3000 polyether polyester copoly type oligomer dihydric alcohol；
(2) component A is prepared：
Polyether polyester copoly type oligomer dihydric alcohol is dehydrated 3- under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa 5h is standby；Polyether polyester copoly type oligomer dihydric alcohol after dehydration is added in reactor, chain extender is sequentially added, hands over Join agent, water, catalyst, foam stabiliser and stabilizer, be warming up to 60-80 DEG C of stirring reaction 4-6h, obtain component A；
(3) component B is prepared：
Isocyanates and stabilizer are put into reactor and be uniformly mixed, the polycyclic oxygen third then added after dehydration Alkane dihydric alcohol, it is warming up to 65-90 DEG C of stirring reaction to-NCO group detected value and ± 0.2% is differed with theoretical value, acquisition component B；
(4) solvent-free polyurethane resin is prepared：
By component A and component B in mass ratio 1:2-2:1 ratio, which is placed in low-pressure casting machine, to be sufficiently mixed solvent-free poly- Urethane resin.
The 3rd goal of the invention of the present invention is to provide a kind of above-mentioned sofa artificial leather middle foaming layer with no-solvent polyurethane tree The application of fat, the solvent-free polyurethane resin are used as the middle foaming layer of soft plentiful sofa artificial leather.
Further scheme, surface layer will be coated on through well-mixed solvent-free polyurethane resin cast in low-pressure casting machine On, base fabric is bonded after 100-150 DEG C of pre-reaction 30-90 second, with reaction 5-10 minutes are continued after 100-150 DEG C, makes its friendship Join curing molding, obtain the soft plentiful sofa synthetic leather of no-solvent type.
Further scheme, the surface layer is the coating surface layer resin slurry LT-80 in release liners, in 130 DEG C of drying and mouldings After obtain.
Production technology of the present invention can reach curing sizing completely in 5-10 minutes, compared to conventional wet production efficiency significantly Improve.Solvent-free polyurethane resin prepared by the present invention is used as the middle foaming layer of sofa synthetic leather, because it is without any Organic solvent, there is full finished leather green, soft, plentiful, its physical property reaches normal temperature and deflects 100,000 Secondary not ftracture, cold-resistant -10 DEG C deflect for 80,000 times and not to ftracture, and peel strength is more than 50N/3cm, 70 DEG C, 95% humidity constant temperature and humidity Under the conditions of 5-7 weeks peel strength retention rate up to 75%.
Compared with prior art, beneficial effects of the present invention are embodied in：
1st, the present invention is using matrix material of the homemade polyether polyester copoly type oligomer dihydric alcohol as component A, and it is not Only there is the soft, low temperature resistant of PPOX polyethers to deflect performance, perforate effect, and introduce after polyester construction with excellent Mechanical strength, so as to the good leather of the sofa artificial leather middle foaming layer opening for ensureing to prepare do not shrink, it is soft it is plentiful, peel off it is strong Degree is high.
2nd, polyether polyester copoly type oligomer dihydric alcohol introduces ester bond and improves resin polarity and surface layer interface knot in the present invention Close more preferable.And use polyether polyester copoly type oligomer dihydric alcohol as component A matrix material than simple polyester diol, poly- Ether dihydric alcohol physical agitation mixing storage stability is good.
3rd, solvent-free polyurethane resin of the invention be by polyhydroxy component A, isocyanate terminated performed polymer component B mixing and Into without any organic solvent.Foamed by the reaction of component A, B and discharge heat, make the sofa artificial leather of preparation soft rich It is full.
4th, during middle foaming layer of the solvent-free polyurethane resin of the invention as synthetic leather, using in dry process production line one Secondary shaping, traditional solvent-borne wet method hair engaging aperture technique is instead of completely.And this solvent-free dry method foam process have cost of labor it is low, Produce and process the features such as energy consumption is low, production process lacks efficiency high.The product meets synthetic leather industry development trend, and more accords with Close green consumption, the demand of environment protection health of consumer.
Embodiment
Below by several specific embodiments, the present invention is further illustrated, but it is to be noted that the present invention Specific material proportion, process conditions and result described in embodiment etc. are merely to illustrate the present invention, can not be limited with this Protection scope of the present invention processed, the equivalent change or modification that every Spirit Essence according to the present invention is made, should all cover In protection scope of the present invention.
Embodiment 1：
(1) preparation of polyether polyester copoly type oligomer dihydric alcohol
Magnetic stirring apparatus, thermometer, N will be housed2The four-hole boiling flask of inlet tube and air-cooling condenser pipe is arranged on sheathing In formula resistance heater, polypropylene oxide glycol (PPG, molecular weight 400), 190 mass of 285 mass parts are loaded into flask Part BDO, 325 mass parts adipic acids, lead to nitrogen 30min with the air in exclusion system.Gradually add under nitrogen protection 140 DEG C or so of heat heating starts dehydrating polycondensation reactions, controls condenser pipe head temperature to be less than 100 DEG C in temperature-rise period.Detection acid Value is less than or equal to add 0.3 mass parts tetraisopropyl titanate reaction 30 minutes during 30mgKOH/g, is gradually heated up being warming up to 240 DEG C. System is maintained at 240 DEG C, vacuum >=0.095MPa, continues cooling after reacting 3h and separates product, preparing hydroxyl value is 56mgKOH/g (molecular weight 2000) polyether polyester copoly type oligomer dihydric alcohol.
(2) component A preparation
Polyether polyester copoly type oligomer dihydric alcohol prepared by (1) is in 100 DEG C, -0.08MPa~-0.1MPa condition Lower dehydration 5h is standby；
3 parts of chain extenders 1,3 are put into after 97 parts of polyether polyester copoly type oligomer dihydric alcohols after dehydration are cooled into 30 DEG C Propane diols, 0.5 part of water, 0.5 part of catalyst BiCAT, 3228,1 parts of foam stabiliser DC-3042,0.2 part of stabilizer Chisorb 622 and 0.3 parts of Chisorb 944,60 DEG C of stirring reaction 4h are warming up to, obtain component A, pack stand-by；
(3) component B preparation
30 parts of isocyanates Wannate MDI-100 are put into reactor and stirred, then after input dehydration 70 parts of polyoxygenated propane dihydric alcohol PPG-2000 and 0.5 part of stabilizer Chinox 1010, be warming up to 80 DEG C of stirring reaction 2h, Extremely-NCO group detected value is (7 ± 0.2) %, obtains component B, packs stand-by；
(4) preparation of solvent-free polyurethane resin
The resin slurry LT-80 of Hefei Anli New Material Polyurethane Co., Ltd.'s production is coated in release liners, 130 DEG C dry It is molded within dry 2 minutes, obtains surface layer；By component A and component B in mass ratio 100：142 ratio is placed in low-pressure casting machine fully Mixing, obtains solvent-free polyurethane resin.
(5) preparation of soft plentiful synthetic leather
The resin slurry LT-80 of Hefei Anli New Material Polyurethane Co., Ltd.'s production is coated in release liners, 130 DEG C dry It is molded within dry 2 minutes, obtains surface layer；It will pour into a mould through well-mixed solvent-free polyurethane resin in low-pressure casting machine and be coated on face Enter 110 DEG C of baking oven pre-reactions 60 seconds on layer, pre-reaction is bonded base fabric after terminating, with continuing 7 points of reaction after 100-150 DEG C Clock, it is molded its crosslinking curing；Wound after curing molding and peel off release liners, obtain sofa with soft plentiful solvent-free Type synthetic leather.
The synthetic leather physical property, which reaches normal temperature and deflects 100,000 times, not to ftracture, and cold-resistant -10 DEG C deflect for 80,000 times and not ftracture, shell It is 60N/3cm from intensity, 70 DEG C, 6 weeks peel strengths are 48N/3cm under the conditions of 95% humidity constant temperature and humidity.
The raw material used in the present embodiment：
1,3-PG is commercially available prod；BiCAT 3228 is the organic bismuth catalyst of the leading chemical company in the U.S.；DC-3042 For the organic silicon modified by polyether foam stabiliser of air chemical company of U.S. production；Chisorb 622, Chisorb 944 and Chinox 1010 is respectively ultra-violet absorber, light stabilizer and the antioxidant of Taiwan double bond Chemical Co., Ltd.；PPG-2000 For the polyoxygenated propane dihydric alcohol of Kunshan national capital Chemical Co., Ltd. production；Wannate MDI-100 give birth to for Yantai Wanhua company The pure diphenylmethylene diisocyanate of production.
Embodiment 2：
(1) preparation of polyether polyester copoly type oligomer dihydric alcohol
Magnetic stirring apparatus, thermometer, N will be housed2The four-hole boiling flask of inlet tube and air-cooling condenser pipe is arranged on sheathing In formula resistance heater, polypropylene oxide glycol (PPG, molecular weight 1000), 200 matter of 300 mass parts are loaded into flask Part BDO, 300 mass parts adipic acids are measured, lead to nitrogen 30min with the air in exclusion system.It is gradual under nitrogen protection 140 DEG C or so of heat temperature raising starts dehydrating polycondensation reactions, controls condenser pipe head temperature to be less than 100 DEG C in temperature-rise period.Detection Acid number is less than or equal to add 0.3 mass parts tetraisopropyl titanate reaction 30 minutes during 30mgKOH/g, is gradually heated up being warming up to 240 ℃.System is maintained at 240 DEG C, vacuum >=0.095MPa, continues cooling after reacting 3h and separates product, preparing hydroxyl value is 374mgKOH/g (molecular weight 3000) PPOX polyethylene terephthalate copolymer type oligomer dihydric alcohol.
(2) component A preparation
Polyether polyester copoly type oligomer dihydric alcohol prepared by (1) is in 100 DEG C, -0.08MPa~-0.1MPa condition Lower dehydration 5h is standby；
1 part of chain extender 1,4- is put into after 99 parts of polyether polyester copoly type oligomer dihydric alcohols after dehydration are cooled into 30 DEG C Butanediol, 0.7 part of water, 0.5 part of catalyst Borchi Kat, 24,1.5 parts of foam stabiliser B-8715-LF2,0.2 part of stabilizer Chisorb 234 and 0.3 part of Chisorb 944,60 DEG C of stirring reaction 4h are warming up to, obtain component A, pack stand-by；
(3) component B preparation
20 parts of isocyanates Wannate MDI-100,10 parts of isocyanates Wannate MDI-50 are put into reactor In and stir, then input dehydration after 70 parts of polyoxygenated propane dihydric alcohol PPG-2000 and 0.5 part of stabilizer Chinox 1010,80 DEG C of stirring reaction 2h are warming up to, extremely-NCO group detected value is (7 ± 0.2) %, obtains component B, packs and treat With；
(4) preparation of solvent-free polyurethane resin
By component A and component B in mass ratio 100：103 ratio, which is placed in low-pressure casting machine, to be sufficiently mixed solvent-free poly- Urethane resin.
(5) preparation of soft plentiful synthetic leather
The resin slurry LT-80 of Hefei Anli New Material Polyurethane Co., Ltd.'s production is coated in release liners, 130 DEG C dry It is molded within dry 2 minutes, obtains surface layer；It will pour into a mould through well-mixed solvent-free polyurethane resin in low-pressure casting machine and be coated on face Enter 110 DEG C of baking oven pre-reactions 60 seconds on layer, pre-reaction is bonded base fabric after terminating, with continuing 7 points of reaction after 100-150 DEG C Clock, it is molded its crosslinking curing；Wound after curing molding and peel off release liners, obtain sofa with soft plentiful solvent-free Type synthetic leather.
The physical property of the synthetic leather, which reaches normal temperature and deflects 100,000 times, not to ftracture, and cold-resistant -10 DEG C deflect for 80,000 times and not ftracture, Peel strength is 55N/3cm, 70 DEG C, 6 weeks peel strengths are 45N/3cm under the conditions of 95% humidity constant temperature and humidity.
The raw material used in the present embodiment：
1,4- butanediols are commercially available prod；Borchi Kat 24 are the organic bismuth catalyst of the leading chemical company in the U.S.； B-8715-LF2 is the foam stabiliser of German Ying Chuan companies production；Chisorb 234, Chisorb 944 and Chinox 1010 The respectively ultra-violet absorber of Taiwan double bond Chemical Co., Ltd., light stabilizer and antioxidant；PPG-2000 is Kunshan national capital The polyoxygenated propane dihydric alcohol of Chemical Co., Ltd.'s production；Wannate MDI-100 and Wannate MDI-50 are Yantai Wanhua The diisocyanate of company's production.
Embodiment 3：
(1) preparation of polyether polyester copoly type oligomer dihydric alcohol
Magnetic stirring apparatus, thermometer, N will be housed2The four-hole boiling flask of inlet tube and air-cooling condenser pipe is arranged on sheathing In formula resistance heater, polypropylene oxide glycol (PPG, molecular weight 400), 243 mass of 243 mass parts are loaded into flask The 3- methyl isophthalic acids of part, 5- pentanediols, 315 mass parts adipic acids, lead to nitrogen 30min with the air in exclusion system.Protected in nitrogen 140 DEG C or so beginning dehydrating polycondensation reactions of heating are gradually heated up under shield, control condenser pipe head temperature to be less than 100 in temperature-rise period ℃.Detection acid number is less than or equal to add 0.3 mass parts tetraisopropyl titanate reaction 30 minutes during 30mgKOH/g, is gradually heated up rising Temperature is to 240 DEG C.System is maintained at 240 DEG C, vacuum >=0.095MPa, continues cooling after reacting 3h and separates product, prepare Hydroxyl value is 44.9mg KOH/g (molecular weight 2500) PPOX polyethylene terephthalate copolymer type oligomer dihydric alcohol.
(2) component A preparation
Polyether polyester copoly type oligomer dihydric alcohol prepared by (1) is in 100 DEG C, -0.08MPa~-0.1MPa condition Lower dehydration 5h is standby；
5 parts of 3- methyl isophthalic acids are put into after 80 parts of polyether polyester copoly type oligomer dihydric alcohols after dehydration are cooled into 30 DEG C, 5- pentanediols MPD, 0.1 part of crosslinking agent glycerine, 1 part of water, 0.5 part of catalyst MB20,1.5 parts of foam stabiliser L-580,0.2 Part stabilizer T inuvin 1130 and 0.3 part of Chisorb 292, is warming up to 60 DEG C of stirring reaction 4h, obtains component A, sealed bundle Fill stand-by；
(3) component B preparation
30 parts of isocyanates Wannate MDI-100,30 parts of Wannate MDI-50 are put into reactor and stirred Uniformly, 50 parts of polyoxygenated propane dihydric alcohol PPG-2000 and 1 part of stabilizer Chinox 1010 after then input is dehydrated, heating To 80 DEG C of stirring reaction 2h, extremely-NCO group detected value is (14.65 ± 0.2) %, obtains component B, packs stand-by；
(4) preparation of solvent-free polyurethane resin
By component A and component B in mass ratio 100：67 ratio, which is placed in low-pressure casting machine, to be sufficiently mixed solvent-free poly- Urethane resin.
(5) preparation of soft plentiful synthetic leather
The resin slurry LT-80 of Hefei Anli New Material Polyurethane Co., Ltd.'s production is coated in release liners, 130 DEG C dry It is molded within dry 2 minutes, obtains surface layer；It will pour into a mould through well-mixed solvent-free polyurethane resin in low-pressure casting machine and be coated on face Enter 110 DEG C of baking oven pre-reactions 60 seconds on layer, pre-reaction is bonded base fabric after terminating, with continuing 7 points of reaction after 100-150 DEG C Clock, it is molded its crosslinking curing；Wound after curing molding and peel off release liners, obtain sofa with soft plentiful solvent-free Type synthetic leather.
The physical property of the synthetic leather, which reaches normal temperature and deflects 100,000 times, not to ftracture, and cold-resistant -10 DEG C deflect for 80,000 times and not ftracture, Peel strength is 65N/3cm, 70 DEG C, 6 weeks peel strengths are 55N/3cm under the conditions of 95% humidity constant temperature and humidity.
The raw material used in the present embodiment：
3- methyl isophthalic acids, 5- pentanediols are commercially available prod；MB20 is that the organo-bismuth of Air Prod ＆ Chem of U.S. production is urged Agent, Tinuvin 1130 are the ultra-violet absorber of BASF Corp. of Germany's production, and Chisorb 292 and Chinox 1010 divide Not Wei Taiwan double bond Chemical Co., Ltd. ultra-violet absorber, light stabilizer and antioxidant；L-580 gives birth to for Mai Tu company of the U.S. The organic silicon modified by polyether foam stabiliser of production；PPG-2000 is the polyoxygenated propane two of Kunshan national capital Chemical Co., Ltd. production First alcohol；Wannate MDI-100 and Wannate MDI-50 are the diisocyanate of Yantai Wanhua company production.

Claims (9)

  1. A kind of 1. sofa artificial leather middle foaming layer solvent-free polyurethane resin, it is characterised in that：It is by component A and component B by Mass ratio 1:2-2:1 mixes；
    The component A is made up of following raw materials by weight portion：
    Polyether polyester copoly type oligomer dihydric alcohol 80-99 parts
    Chain extender 1-5 parts
    Crosslinking agent 0-1 parts
    Water 0.1-3 parts
    Catalyst 0.02-1 parts
    Foam stabiliser 0-2 parts
    Stabilizer 0.5-2.0 parts；
    The component B is made up of following raw materials by weight portion：
    Polypropylene oxide glycol 40-70 parts
    Isocyanates 30-60 parts
    Stabilizer 0.5-1.0 parts.
  2. A kind of 2. sofa artificial leather middle foaming layer solvent-free polyurethane resin according to claim 1, it is characterised in that：Institute It is to be esterified dehydration condensation by weight by following component and be made to state polyether polyester copoly type oligomer dihydric alcohol, its molecule Measure as 2000-3000,
    Adipic acid 30-60 parts
    Small molecule dihydric alcohol 20-40
    Polyether Glycols 20-40 parts
    Catalyst 0.02-0.06 parts.
  3. A kind of 3. sofa artificial leather middle foaming layer solvent-free polyurethane resin according to claim 2, it is characterised in that：Institute State the polypropylene oxide glycol that polyether Glycols are molecular weight 400-2000；
    The catalyst is butyl titanate or tetraisopropyl titanate；
    The small molecule glycol chain extender is ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,4- butanediols, 1,5- penta 2 Alcohol, neopentyl glycol, diglycol, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD, 1,4 cyclohexane dimethanol quinhydrones are double （2- ethoxys）One or more in ether.
  4. A kind of 4. sofa artificial leather middle foaming layer solvent-free polyurethane resin according to claim 1, it is characterised in that：
    The crosslinking agent is one or both of glycerine, trimethylolpropane；
    The molecular weight of the polypropylene oxide glycol is 1000-3000；
    The catalyst is delaying type catalyst；
    The foam stabiliser is polyether-modified organic silicon surfactant；
    The stabilizer is ultra-violet absorber, hindered amine light stabilizer or antioxidant；
    The isocyanates is 4,4 '-methyl diphenylene diisocyanate, 2,4- methyl diphenylene diisocyanates and 4,4 '-two The mixture of methylenebis phenyl isocyanate, or methyl diphenylene diisocyanate and polyphenyl polymethylene polyisocyanates Mixture.
  5. A kind of 5. sofa artificial leather middle foaming layer solvent-free polyurethane resin according to claim 4, it is characterised in that：
    The delaying type catalyst is selected from BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228, Borchi Kat 22, Borchi Kat 24, BiCAT 4130, BiCAT 4232, the phenol of MB20 and above-mentioned organometallic catalysts Salt, formates, hydrochloride one kind therein；
    The polyether-modified organic silicon surfactant include US Air gasification DC-193, DC-2525 of work, DC-2585, B-8715-LF2, B-8726-LF2, B-8738-LF2 of DC-3042, DC-3043, DC-5043 or German Ying Chuan companies, or it is beautiful L-580, L-818, L-3002, L-3415 of Mai Tu company of state；
    The ultra-violet absorber is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234；Hindered amines light is stable Agent is 292,622,770,944,5050,5060 or 5151；Antioxidant is 245,1010,1035,1076,1098 or 3114.
  6. 6. a kind of preparation method of sofa artificial leather middle foaming layer solvent-free polyurethane resin according to claim 1, its It is characterised by：Comprise the following steps：
    （1）Prepare polyether polyester copoly type oligomer dihydric alcohol：
    Magnetic stirring apparatus, thermometer, N will be housed2The four-hole boiling flask of inlet tube and air-cooling condenser pipe is arranged on sheathing formula electricity Hinder in heater, polyether Glycols, small molecule dihydric alcohol, adipic acid are added into flask, the air led in nitrogen exclusion flask； Then heating is gradually heated up under nitrogen protection and carries out dehydrating polycondensation reaction, and the head temperature of condenser pipe is controlled in temperature-rise period Less than 100 DEG C；Detection acid number adds catalyst when being not more than 30mgKOH/g continues after reacting 30 minutes, then is gradually heated up heating up To 240 DEG C, the MPa of vacuum >=0.095, continuing reaction makes hydroxyl value reach 36-56 mg KOH/g, and it is 2000- that molecular weight, which is made, 3000 polyether polyester copoly type oligomer dihydric alcohol；
    （2）Prepare component A：
    It is standby that polyether polyester copoly type oligomer dihydric alcohol is dehydrated under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa to 3-5h With；Polyether polyester copoly type oligomer dihydric alcohol after dehydration is added in reactor, sequentially adds chain extender, crosslinking Agent, water, catalyst, foam stabiliser and stabilizer, 60-80 DEG C of stirring reaction 4-6h is warming up to, obtains component A；
    （3）Prepare component B：
    Isocyanates and stabilizer are put into reactor and be uniformly mixed, the PPOX two then added after dehydration First alcohol, it is warming up to 65-90 DEG C of stirring reaction to-NCO group detected value and ± 0.2% is differed with theoretical value, acquisition component B；
    （4）Prepare solvent-free polyurethane resin：
    By component A and component B in mass ratio 1:2-2:1 ratio, which is placed in low-pressure casting machine, is sufficiently mixed to obtain no-solvent polyurethane Resin.
  7. 7. a kind of application of sofa artificial leather middle foaming layer solvent-free polyurethane resin as claimed in claim 1, its feature exist In：The solvent-free polyurethane resin is used as the middle foaming layer of soft plentiful sofa artificial leather.
  8. 8. application according to claim 8, it is characterised in that：Will be through well-mixed solvent-free poly- ammonia in low-pressure casting machine Ester resin-cast is bonded base fabric coated on surface layer after 100-150 DEG C of pre-reaction 30-90 second, with after 100-150 DEG C of continuation 5-10 minutes are reacted, its crosslinking curing is molded, obtains the soft plentiful sofa synthetic leather of no-solvent type.
  9. 9. application according to claim 8, it is characterised in that：The surface layer is the coating surface layer resin slurry in release liners LT-80, obtained after 130 DEG C of drying and mouldings.
CN201710856325.3A 2017-09-20 2017-09-20 A kind of sofa artificial leather middle foaming layer solvent-free polyurethane resin and preparation method thereof Pending CN107602802A (en)

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CN109749043A (en) * 2018-12-29 2019-05-14 浙江华峰合成树脂有限公司 Height removing leather solvent-free polyurethane resin and its preparation method and application
CN109898343A (en) * 2019-02-26 2019-06-18 合肥安利聚氨酯新材料有限公司 Super soft use for synthetic leather no-solvent polyurethane intermediate layer resin of one kind and preparation method thereof
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CN111138619A (en) * 2019-12-18 2020-05-12 福建成杰高分子材料有限公司 Preparation method of solvent-free ultraviolet curing polyurethane for synthetic leather
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CN108485242B (en) * 2018-03-16 2020-12-04 上海汇得科技股份有限公司 High-astringency wet-process polyurethane resin and preparation method thereof
CN109749043A (en) * 2018-12-29 2019-05-14 浙江华峰合成树脂有限公司 Height removing leather solvent-free polyurethane resin and its preparation method and application
CN109749043B (en) * 2018-12-29 2021-07-16 浙江华峰合成树脂有限公司 Solvent-free polyurethane resin for high-stripping leather and preparation method and application thereof
CN109898343A (en) * 2019-02-26 2019-06-18 合肥安利聚氨酯新材料有限公司 Super soft use for synthetic leather no-solvent polyurethane intermediate layer resin of one kind and preparation method thereof
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CN111138619A (en) * 2019-12-18 2020-05-12 福建成杰高分子材料有限公司 Preparation method of solvent-free ultraviolet curing polyurethane for synthetic leather
CN112431029A (en) * 2020-11-03 2021-03-02 安徽安利材料科技股份有限公司 High-environmental-protection solvent-free polyurethane synthetic leather for sofa furniture and preparation method thereof
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Application publication date: 20180119